Preparation of copper arsenite and its application in purification of copper electrolyte

The preparation of copper arsenite with arsenic trioxide was presented and its application in the purification of copper electrolyte was proposed. The variables of n（OH^-）/n（As）, n（Cu）/n（As）, NaOH concentration, reaction temperature and pH value have some effects on the yield of copper arsenite. The optimum conditions of preparing copper arsenite are that the molar ratio of alkali to arsenic is 2：1, NaOH concentration is 1 mol/L, the molar ratio of copper to arsenic is 2：1, pH value is 6.0 and reaction temperature is 20℃. The yield of copper arsenite is as high as 98.65% under optimum conditions and the molar ratio of Cu to As in the product is about 5：4. The results of the purification experiments show that the removal rate of antimony and bismuth is 53.85% and 53.33% respectively after 20g/L copper arsenite is added. The purification of copper electrolyte with copper arsenite has the advantages of simple technique, good purification performance and low cost.     

砷化氢析出电势的探讨

据热力学参数,计算得到砷酸、亚砷酸、单的出砷化氢的标准平衡电势值分别为０．１４４Ｖ,０．００５Ｖ,－０．２３８Ｖ。在铜电解液净化工序中,砷酸优先于亚砷酸析出砷化氢,当阴极电势足够负时,帮人同放电析出砷化氢。计算结果与实测结果基本吻合,均表明砷化氢析出的标准平衡电势值正于－０．６０８Ｖ。在铜妆液工序中,采用控制阴极电势脱部胂电积法,能有效抑制砷化氢的析出。     

二段脱铜液还原结晶法脱砷新工艺

对铜电解液脱砷方法进行研究,提出以二段脱铜液为原料,采用SO2还原结晶法脱砷新工艺。在二段脱铜液中通入SO2,将其中的As(Ⅴ)还原成As(Ⅲ),还原后的溶液通过蒸发结晶析出As2O3,达到二段脱铜液脱砷的目的。结果表明:当As(Ⅴ)浓度为12.41 g/L、H2SO4浓度为253.00 g/L、反应温度为60℃时,向二段脱铜液中通入SO290 min后静置90 min,二段脱铜液中As(Ⅴ)的还原率达到94.54%。还原后的溶液进行蒸发结晶,当蒸发前与结晶后的体积比(V0:V1)为3.5时,砷的脱除率达到91.33%,结晶产物为As2O3。与传统脱砷工艺相比,新工艺具有操作简单、成本低廉及砷的脱除效果明显等优势。     

Sb在铜电解液净化中的应用

介绍了Sb在铜电解液净化中的应用。铜阳极泥分银渣 (含Sb 2 1.35 %)以及由Sb2 O3 和BaSO4 合成的吸附剂能选择性吸附电解液中的As,Sb ,Bi。在确保电解液主要成分不变的情况下 ,不论是分银渣还是合成吸附剂都能从铜电解液中吸附 90 %Bi,80 %Sb及部分As。在讨论吸附机理的同时 ,还研究了阳极铜含Sb对电解过程杂质在阳极泥和电解液之间的分配比例的影响。发现提高Sb在阳极铜里的相对含量可增大电解过程As,Sb ,Bi进入阳极泥的比例 ,从而为铜电解净液寻找了一条方便经济的途径。     

铜电解液中砷的还原及脱除(英文)

探讨了反应温度、H2SO4浓度、CuSO4浓度、反应时间、SO2气流量等因素对SO2还原铜电解液中As(Ⅴ)的影响,并对浓缩共晶作用下铜电解液中As(III)的脱除行为进行了研究。研究表明:As(V)还原率随着反应温度和H2SO4浓度的升高而降低,随着SO2气流量的增大及反应时间的延长而升高。当反应温度为65°C,H2SO4浓度为203g/L,CuSO4浓度为80g/L,SO2流量为200mL/min,反应时间为2h时,铜电解液中As(Ⅴ)还原率为92%;铜电解液中的As(V)还原后,将铜电解液浓缩至H2SO4浓度为645g/L时,As、Cu、Sb、Bi脱除率分别达到83.9%,87.1%,21%,84.7%.XRD分析结果表明:结晶产物中含有As2O3和CuSO4·5H2O等物相。     

Recovering Bi and Sb from electrolyte in copper electrorefining

The separation of antimony and bismuth in copper electrorefining is somewhat difficult and costly. An ion-exchange technique for the removal of the metals from the electrolyte has been practiced recently, although the metals recovered require further processing. Sumitomo Metal Mining has developed a process to recover antimony and bismuth directly from the eluant by an electrowinning process using a mixture of sulfuric acid and sodium chloride as an eluant for the desorption from the resin. The content of bismuth in the antimony metal recovered by this process was less than 0.2%, while the content of antimony in the bismuth metal was less than 0.4%. K. Ando earned his M.Sc. in metallurgical engineering at Kumamoto University in 1986. He is currently a senior scientist at Sumitomo Metal Mining Company. N. Tsuchida earned his Ph.D. in mineral science at Murdoch University, Western Australia, in 1986. He is currently manager of the Niihama nickel refinery at Sumitomo Metal Mining Company.     

Recovery of bismuth and antimony metals from pressure-leaching slag

The leaching behavior of metals from a pressure-leaching slag was investigated using a desulphurization-leaching-hydrolysis process for the recovery of bismuth and antimony.Various parameters were studied,including the amount of acid added,temperature,time,addition of NaCl and solid-liquid ratio in the leaching process.The experimental results show that the contents of bismuth and antimony are mostly enriched in the process of kerosene desulphurization.More than 98％ Sb and 96％ Bi are extracted under the determined conditions.In the process of hydrolysis,the precipitation rates of bismuth and antimony are 97.80％ and 94.59％,respectively.Under the optimum experimental conditions,the recovery rate of bismuth and antimony can be up to 95.80％ and 90.80％,respeoively.     

CAUSE OF FORMATION OF NODULAR COPPER PARTICLES ON ELECTROREFINED COPPER SUBSTRATE

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Removal of Antimony and Bismuth from Copper Electrorefining Electrolyte: Part II—An Investigation of Two Proprietary Solvent Extraction Extractants

Antimony and bismuth recovery from copper electrorefining electrolyte could reduce the impacts of these problem elements and produce a new primary source for them. Two proprietary phosphonic acid ester extractants were examined (REX-1 and REX-2) for the removal of antimony and bismuth from copper electrorefining electrolytes. Experimentation included shakeout and break tests to determine the basic parameters for the extractants in terms of maximum loading, break times, and extraction and stripping efficiency. Five permutations of extractant mixtures (100 wt.% REX-1 and 25 wt.%, 50 wt.%, 75 wt.% and 100 wt.% REX-2) were studied. It was determined that REX-2 was able to extract Sb and Bi from the electrolyte, but required some mixture with REX-1 to better facilitate stripping with 400 g/L sulfuric acid. The laboratory electrorefining electrolyte containing glue had faster disengagement times than a synthetic solution without glue.     

Preparation of clarificant for glass from As-Sb dust

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铜阳极泥选冶联合工艺有价金属走向考察及改进建议

铜阳极泥是资源综合回收的优选对象,分析各有价金属的分散情况对后续的回收有着指导性的方向作用。铜阳极泥选冶联合工艺较为成熟,具有不断外延拓展金属回收的空间。针对4000 t铜阳极泥物料的生产数据,考察了该工艺有价金属的走向,统计分析了金、银、硒、碲、铅、锑、铋、铜等在工艺流程中的分布率,摸清了有价金属主要分散情况。分析表明,金、银、硒、碲最大的分散点均为浮选尾矿,分别占分散总量的67%、37%、34%、58%,确定为重点管控对象。并结合统计分析结果对提高金、银、硒、碲回收率及铅、锑、铋、铜的回收提出了改进建议。     

Extraction of arsenic from arsenic-containing cobalt and nickel slag and preparation of arsenic-bearing compounds

The arsenic extraction from the arsenic-containing cobalt and nickel slag, which came from the purification process of zinc sulfate solution in a zinc smelting factory, was investigated. The alkaline leaching method was proposed according to the mode of occurrence of arsenic in the slag and its amphoteric characteristic. The leaching experiments were conducted in the alkaline aqueous medium, with bubbling of oxygen into the solution, and the optimal conditions for leaching arsenic were determined. The results showed that the extraction rate of arsenic was maximized at 99.10% under the optimal conditions of temperature 140 °C, NaOH concentration 150 g/L, oxygen partial pressure 0.5 MPa, and a liquid-to-solid ratio 5:1. Based on the solubilities of As₂O₅, ZnO and PbO in NaOH solution at 25 °C, a method for the separation of As in the form of sodium arsenate salt from the arsenic-rich leachate via cooling crystallization was established, and the reaction medium could be fully recycled. The crystallization rate was confirmed to reach 88.9% (calculated on the basis of Na₃AsO₄) upon a direct cooling of the hot leachate down to room temperature. On the basis of redox potentials, the sodium arsenate solution could be further reduced by sulfur dioxide (SO₂) gas to arsenite, at a reduction yield of 92% under the suitable conditions. Arsenic trioxide with regular octahedron shape could be prepared successfully from the reduced solution, and further recycled to the purification process to purify the zinc sulfate solution. Also, sodium arsenite solution obtained after the reduction of arsenate could be directly used to purify the zinc sulfate solution. Therefore, the technical scheme of alkaline leaching with pressured oxygen, cooling crystallization, arsenate reduction by SO₂ gas, and arsenic trioxide preparation, provides an attractive approach to realize the resource utilization of arsenic-containing cobalt and nickel slag.     

Selective removal of As from arsenic-bearing dust rich in Pb and Sb

The selective removal of arsenic from arsenic-bearing dust containing Pb and Sb in alkaline solution was studied. The influence of NaOH concentration, temperature, leaching time, liquid to solid ratio, and the presence of elemental sulfur on the dissolution of As, Sb and Pb in NaOH solution was investigated. The results indicate that the presence of elemental sulfur can effectively prevent leaching of lead and antimony from arsenic. The Sb₂O₃, As₂O₃ and Pb₅(AsO₄)₃OH in the raw material convert to NaSb(OH)₆ and PbS in the leaching residue, while arsenic is leached out as As(III) or As(V) ions in the leaching solution. Arsenic leaching efficiency of 99.84% can be achieved under the optimized conditions, while 97.82% of Sb and 99.97% of Pb remain in the leach residue with the arsenic concentration of less than 0.1%. A novel route is presented for the selective removal of arsenic and potential recycle of lead and antimony from the arsenic-bearing dust leached by NaOH solutions with the addition of elemental sulfur.     

用钙、镁和锑深度除铋

为了实现铅的深度除铋,对钙、镁添加量以及锑处理和温度对铅中除铋深度的影响进行研究,并对除铋机理进行讨论。结果表明,当钙、镁添加量分别达到0.112%和0.395%时,在330℃时不用添加锑就可以使产品的含铋量降低到0.001%。维持镁加入量为0.155%,当钙添加量低于0.09%（包晶反应点的浓度）,随后采用锑处理可以很容易使铋含量降到0.001%;但当钙添加量大于0.09%时,锑处理对除铋的作用效果越来越差。     

Sulfide smelting using Ausmelt technology

Over the past decade, Ausmelt has been developing the top submerged lancing process for the smelting of sulfidic ores to recover such metals as copper, lead, silver, tin, antimony, and nickel as well as for separation of minor elements such as arsenic, antimony, and bismuth. Development has taken place in Ausmelt’s pilot plant in Dandenong, near Melbourne, Australia. A number of projects have proceeded to commercial-scale operation. This paper reviews developments at both the pilot and commercial scales.     

稀土在钢中的应用

稀土能与钢液中的氧、硫产生极强的结合、与磷、砷、锑、铋、铅、铜等低熔点杂质发生交互作用，同时能改善夹杂物的形态和大小，细化晶粒，均匀分布。     

Application and mechanism of Fenton-like iron-based functional materials for arsenite removal

Between the two major arsenic-containing salts in natural water, arsenite (As(III)) is far more harmful to human and the environment than arsenate (As(V)) due to its high toxicity and transportability. Therefore, preoxidation of As(III) to As(V) is considered to be an effective means to reduce the toxicity of arsenic and to promote the removal efficiency of arsenic. Due to their high catalytic activity and arsenic affinity, iron-based functional materials can quickly oxidize As(III) to As(V) in heterogeneous Fenton-like systems, and then remove As(V) from water through adsorption and surface coprecipitation. In this review, the effects of different iron-based functional materials such as zero-valent iron and iron (hydroxy) oxides on arsenic removal are compared, and the catalytic oxidation mechanism of As(III) in heterogeneous Fenton process is further clarified. Finally, the main challenges and opportunities faced by iron-based As(III) oxidation functional materials are prospected.     

控制阴极电势电积法脱铜砷

在净化铜电解废液工艺流程中，控制阴极电势值，使铜砷优先析出，并抑制氢气与砷化氢的析出，以达到净化电解液的目的。控制阴极电势脱铜砷电积法的脱铜电流效率达到８０％以上，电积后液中铜含量小于０．５ｇ／Ｌ，砷含量小于１ｇ／Ｌ，该方法具有节能与环保双重效益。     

铜电解过程中As(Ⅲ)净化作用及其氧化动力学

研究铜电解过程中As(Ⅲ)初始浓度对电解液净化的影响及其氧化动力学。结果表明:当电流密度为235A/m2、电解时间为168 h、电解液中As(Ⅲ)初始浓度为0时,总As浓度(TAs)从10.00 g/L增加至10.62 g/L,Sb的浓度从0.40 g/L增加至0.45 g/L,Bi的浓度从0.22 g/L增加至0.24 g/L;当As(Ⅲ)初始浓度为5.00 g/L时,As(Ⅲ)从5.00 g/L下降至1.80 g/L,TAs从10.00 g/L下降至9.70 g/L,Sb的浓度从0.40 g/L下降至0.26 g/L,Bi的浓度从0.22 g/L下降至0.18 g/L;当电流密度为235 A/m2,电解时间为144 h时,As(Ⅲ)的浓度从7.62 g/L下降至3.71g/L,TAs浓度约为11.16 g/L,Sb的浓度从0.22 g/L微增至0.26 g/L,Bi的浓度为0.086 g/L。在铜电解过程中,As(Ⅲ)能够抑制电解液中TAs、Sb和Bi的浓度的增加,具有净化铜电解液的作用;As(Ⅲ)不断被氧化,其氧化反应符合一级反应动力学规律,活化能为46.11 kJ/mol。     

超声强化单斜磁黄铁矿从铜烟灰中选择性硫化沉淀铜离子

在单斜磁黄铁矿(MPr)处理废水重金属离子过程中表面产生的硫化物钝化膜严重阻碍进一步反应.采用超声波技术辅助MPr回收铜离子.XPS分析结果表明,反应过程中MPr表面存在CuS产物.XRD和SEM分析结果表明,在超声条件下颗粒表面的CuS被剥离.动力学结果表明,常规和超声条件下的反应均符合Avrami模型.在超声条件下...